New formulation methodology for distortional thermosets

ABSTRACT

Methods and formulations for distortional thermosets are disclosed that display enhanced composite mechanical performances and robust sorption resistance. The composition includes an epoxy resin of formula (I): 
     
       
         
         
             
             
         
       
     
     and a diamine curing agent. The resultant distortional thermoset compositions possess superior out-life requirements and advantageous reaction kinetics for preparing prepreg compositions and materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/963,745 filed Aug. 9, 2013. The above-mentioned application is herebyincorporated by reference.

FIELD

The disclosure relates generally to methods and formulations fordistortional thermosets.

BACKGROUND

Thermoset polymers form the matrix in filled plastics andfiber-reinforced composites used in many different products. Thermosetsare used extensively as adhesives, molding compounds and surfacecoatings. Three stages are typically used in the processing of thermosetpolymers. In the A-stage the resin is still soluble and fusible. In theB-stage, thermosets are nearly insoluble but remain thermoplastic.Though the B-stage material exists in a molten state, this material isrelatively short-lived owing to the fact that the temperature used topromote flow also causes the material to crosslink. The C-stagerepresents the final stage of polymerization, wherein the polymerundergoes crosslinking under the controlled influence of heat andpressure over time. The resultant thermosets build their final structureduring this processing, forming a three-dimensional internal structuralnetwork of highly-crosslinked polymer chains. The final thermosetmaterial is insoluble and not thermally reformable.

Many composite structures are composed of fibers and thermoset polymersthat are generally epoxies. Because of the present restrictions on fiberorientations, the composites containing such thermosets typically deformmatrix by dilatation when a mechanical load is applied. Since dilationis an elastic response to the applied load, these composites display lowstrength, high weight, and/or other limited mechanical performanceattributes. Thus, composite materials that include fiber orientationscoupled with thermosets have improved distortional properties whensubjected to loads. U.S. Pat. No. 7,985,808 to Christensen et al.describes thermosets having a distortional matrix intended for use incomposites with the proper fiber orientation, which is hereinincorporated by reference in its entirety. A variety of engineeringcomponents and structures rely upon distortional thermosets afforded bycertain epoxy resin composites.

All epoxies deform by either dilation and/or distortion. Dilation iscontrolled through non-bonded forces at the molecular level within theepoxy structure and is generally similar among various epoxies. Yet thedistortional attributes of epoxies can be highly varied depending uponthe chemical formulation of epoxies.

The matrix of epoxy composites will either dilate or distort dependingon the nature of the loading and, most importantly, the fiberorientation. The fiber orientations of prepreg materials will force thematrix material to dilate. New design concepts for materials havingoptimal fiber orientation are exploring the benefits of distorting thematrix as a means for improved performance for these materials. Suchdesign considerations require new epoxy matrix materials havingoptimized distortion attributes.

Yet distortional thermosets are affected by a variety of environmentalelements that can compromise their reliability in epoxy-basedengineering components and structures. Polymer or material changescaused by the service environment may lead to premature failure.Examples of such polymer changes and service life conditions include:thermo-oxidation; photo-oxidation (for example, from sunlight/UV-light);cyclic fatigue (for example, from vibration); physical aging (forexample, densification); erosion; environmental stress-crackingresistance (ESCR); and sorption of water, fluids, etc. The effect ofdifferent service life conditions may be synergistic, leading tosurprisingly quick failures. Polymer performance in these areas may berelated to both the degree of crosslinking and the chemical nature orpolarity of the amorphous polymer. For example, sorption of a fluid bythe cured epoxy may lead to chemical changes as well as mechanicalchanges. For fully cured epoxies, fluid sorption has led to failures,often interrelated, from: swelling, modulus loss, strength loss, stresscracking (ESCR), weight gain, gloss loss, hardness loss, adhesion lossand coloration. Such service environment effects also affectdistortional thermosets, where the desired mechanical performanceattributes of these materials can be compromised.

BRIEF SUMMARY

In a first respect, a composition having a von Mises strain of at least0.300 is disclosed, wherein the composition includes an epoxy resin offormula (I):

and a diamine curing agent.

In a second respect, composition having an absorption of fluid being nomore than about 1% (wt) is disclosed, wherein the composition includesan epoxy resin of formula (I) and a diamine curing agent.

In a third respect, a prepreg composition is disclosed that includes aplurality of fibers, and a thermoset composition. The thermosetcomposition comprises an epoxy resin of formula (I) and a diamine curingagent.

In a fourth respect, a method of preparing a prepreg composition isdisclosed. The method includes the step of applying a thermosetcomposition to a plurality of fibers. The thermoset compositioncomprising an epoxy resin of formula (I) and a diamine curing agent.

These and other features, objects and advantages will become betterunderstood from the description that follows.

DETAILED DESCRIPTION

The composition and methods now will be described more fullyhereinafter. These embodiments are provided in sufficient written detailto describe and enable a person having ordinary skill in the art to makeand use the claims, along with disclosure of the best mode forpracticing the claims, as defined by the claims and equivalents thereof.

Likewise, modifications and other embodiments of the methods describedherein will come to mind to one of skill in the art having the benefitof the teachings presented in the foregoing descriptions. Therefore, itis to be understood that the disclosure is not to be limited to thespecific embodiments disclosed and that modifications and otherembodiments are intended to be included within the scope of the appendedclaims. Although specific terms are employed herein, they are used in ageneric and descriptive sense only and not for purposes of limitation.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of skill in the art.Although any methods and materials similar to or equivalent to thosedescribed herein can be used in the practice or testing of the claims,the exemplary methods and materials are described herein.

Moreover, reference to an element by the indefinite article “a” or “an”does not exclude the possibility that more than one element is present,unless the context clearly requires that there be one and only oneelement. The indefinite article “a” or “an” thus usually means “at leastone.”

The term “about” means within a statistically meaningful range of avalue or values such as a stated concentration, length, molecularweight, pH, time frame, temperature, pressure or volume. Such a value orrange can be within an order of magnitude, typically within 20%, moretypically within 10%, and even more typically within 5% of a given valueor range. The allowable variation encompassed by “about” will dependupon the particular system under study.

The chemical structures described herein are named according to IUPACnomenclature rules and include art-accepted common names andabbreviations where appropriate. The IUPAC nomenclature can be derivedwith chemical structure drawing software programs, such as ChemDraw®(PerkinElmer, Inc.), ChemDoodle® (iChemLabs, LLC) and Marvin (ChemAxonLtd.). The chemical structure controls in the disclosure to the extentthat an IUPAC name is misnamed or otherwise conflicts with the chemicalstructure disclosed herein.

New distortional thermosets are disclosed that provide unexpectedlysuperior resistance to environmental contaminants and fluid sorptionwhile preserving the enhanced mechanical performance attributesassociated with previous distortional thermosets. The new formulationsfor the distortional thermosets also afford superior shelf-life storagecapabilities at ambient temperatures. As detailed below, the newformulations have superior out-life requirements, wherein theformulations do not undergo premature hardening or curing at ambienttemperature. Furthermore, the formulations provide advantageous reactionkinetics for preparing prepreg composites. These and other features ofthe new formulations and the methods directed thereto are more fullydescribed below.

The new distortional thermosets are based upon an epoxy resin having thestructure of formula (I):

wherein the glycidyl ether moieties are independently selected to becoupled to their respective phenyl moieties at either the ortho-, meta-or para-positions relative to the coupled, phenylmethylenyl moiety. TheIUPAC name for formula (I) corresponds to2-{a-[(4-{[b-(oxiran-2-yloxy)phenyl]methyl}phenyl)methyl]phenoxy}oxirane,wherein a and b are independently designated 2, 3 or 4 depending uponthe isomer. Compositions of compounds of formula (I) can includepurified homogeneous preparations of any one of the six possible isomerforms, preparations of racemic mixtures including at least two or moreof the isomer forms, and preparations of racemic mixtures including allsix possible isomer forms.

Thus, isomers of formula (I), include formulas (Ia) through (If), asillustrated below in Table I:

TABLE I Isomers of Formula (I). Formula Structure IUPAC Name (Ia)

1,4-bis(2-(oxiran-2- yloxy)benzyl)benzene (Ib)

2-(2-(4-(3-(oxiran-2- yloxy)benzyl)benzyl) phenoxy)oxirane (Ic)

2-(2-(4-(4-(oxiran-2- yloxy)benzyl)benzyl) phenoxy)oxirane (Id)

1,4-bis(3-(oxiran-2- yloxy)benzyl)benzene (Ie)

2-(3-(4-(4-(oxiran-2- yloxy)benzyl)benzyl) phenoxy)oxirane (If)

1,4-bis(4-(oxiran-2- yloxy)benzyl)benzene

The synthesis of compounds of formula (I) are known in the art; see, forexample, M. Kodomari and S. Taguchi, J. Chem. Research (S) pp. 240-241(1996), the contents of which are herein incorporated by reference inits entirety. Because the synthesis of epoxy resins of formula (I)typically use the bisphenol of xylene as a starting material, ashort-hand nomenclature for epoxy resins of formula (I) is BisX. As usedherein, BisX represents any one of the isomers encompassed by formula(I), including formulas (Ia)-(If), as well as racemic mixtures of two ormore such isomers encompassed by formula (I), including formulas(Ia)-(If).

The thermoset formulations disclosed herein include a multi-amine, suchas a diamine, to promote curing or crosslinking of the epoxy resins offormula (I). The thermoset formulations can include a range ofstoichiometric ratios of amine hydrogens to epoxide groups, varying froma balanced stoichiometry of about 1:1 to an amine starved stoichiometryof about 0.6:1.0. The thermoset formulations can include fractionalvalues within the range of stoichiometric ratios of amine hydrogens toepoxide groups, such as about 0.95:1.0, about 0.90:1.0, about 0.85:1.0,about 0.75:1.0, about 0.70:1.0, and about 0.65:1.0. A variety ofdiamines are known in the art as curing agents. Examples of diamines ascuring agents are provided in Table II. These monomeric precursorsprovide superior distortional matrices when used as curing agents withthe epoxy resins of formula (I).

TABLE II Exemplary Diamine Curing Agents. Formula Structure Name(Shorthand) (II)

4,4′-sulfonyldianiline (44DDS) (III)

4,4′-methylenedianiline (MDA) (IV)

4,4′-oxydianiline (44ODA) (V)

3,3′-(1,3-phenylenebis(oxy))- dianiline (APB133) (VI)

4,4′-(1,3-phenylenebis(oxy))- dianiline (TPE-R) (VII)

4,4′-methylenebis(2-ethyl- aniline) (VIII)

3,3′-((2,2-dimethylpropane- 1,3-diyl)bis(oxy))dianiline (DANPG) (IX)

4,4′-(1,4-phenylenebis- (propane-2,2-diyl))dianiline (X)

3-(4-(4-aminobenzyl)- benzyl)aniline (XI)

4,4′-(1,4- phenylenebis(propane-2,2- diyl))bis(2,6-dimethylaniline)(EPON-1062-M) (XII)

4,4′-(1,4-phenylenebis(oxy))- dianiline (TPE-Q) (XIII)

3,3′-((propane-2,2-diylbis- (4,1phenylene))bis(oxy))- dianiline (XIV)

3,3′-sulfonyldianiline (33DDS) (XV)

4,4′-methylenebis(cyclo- hexan-1-amine) (XVI)

4,4′-thiodianiline (ASD) (XVII)

3,3′-((sulfonylbis(4,1- phenylene))bis(oxy))dianiline (m-BAPS) or(3BAPS) (XVIII)

4,4′-(1,4-phenylenedi- sulfonyl)dianiline (XIX)

4,4′-(pentane-1,5-diylbis- (oxy))dianiline (DA5MG) (XX)

4,4′-([1,1′-biphenyl]-4,4′- diylbis(oxy))dianiline (BAPB) (XXI)

4,4′-(1,3-phenylenebis- (propane-2,2-diyl))bis (2,6-diisopropylaniline)(XXII)

4,4′-(1,3-phenylenebis- (propane-2,2-diyl))dianiline (Bisaniline M)(XXIII)

4,4′-((sulfonylbis(4,1- phenylene))bis(oxy))dianiline (BAPS) (XXIV)

4,4′-((propane-2,2-diylbis- (4,1phenylene))bis(oxy))- dianiline (BAPP)(XXV)

4,4′-disulfanediyldianiline

The diamine curing agents of Table II can be characterized in terms ofcertain properties, such as distortion behavior (for example, von Misesstrain value), controllability of reaction kinetics of curing; fluidsorption resistance; resin modulus; glass transition temperature;melting point for blending; and health risks (for example, carcinogenicproperties). Table III presents these attributes and their relativeranking for each of the diamine curing agents of Table II.

TABLE III Criteria and Properties of Exemplary Diamine Curing Agents.Reaction MEK Adequate Melting Good Control Resistance Adequate GlassPoint for for (low free Resin Transition for Health Formula DistortionCuring volume) Modulus Temp. Blending Concerns II 2 5 4 4 5 4 5 III 2 34 4 4 4 1 IV 2 2 4 4 4 4 3 V 5 3 4 4 3 4 4 VI 5 2 4 4 3 4 4 VII 2 2 2 44 4 3 VIII 5 1 3 2 2 4 3 IX 5 2 2 3 3 3 3 X 5 2 4 3 3 3 3 XI 5 3 1 3 3 33 XII 5 2 4 3 3 3 3 XIII 4 3 3 2 2 2 3 XIV 2 2 4 4 4 4 4 XV 2 1 3 3 3 43 XVI 3 4 4 3 3 3 3 XVII 4 4 3 2 2 2 3 XVIII 5 4 4 4 4 1 3 XIX 4 2 2 2 24 3 XX 4 3 4 4 3 2 3 XXI 4 3 1 3 3 2 3 XXII 4 3 2 3 3 3 3 XXIII 4 4 3 22 2 3 XXIV 4 5 3 2 2 2 3 XXV 3 5 4 3 3 3 3

With respect to each of the performance attributes identified in TableIII, each of the diamine curing agents has a relative ranking on a scalefrom 1 to 5, where a ranking score of “1” (where applicable) refers to aparticular performance attribute that is least preferred with respect tothat single attribute when compared to other diamine curing agents andwhere a ranking score of “5” refers to a particular performanceattribute that is most preferred with respect to that single attributewhen compared to other diamine curing agents. One skilled in the artwill recognize that the selection of a given diamine curing agent in athermoset formulation will depend upon the relative importance of eachperformance attribute of the diamine curing agent in relation to theparticular application for which the thermoset formulation will be used.Among distortional thermoset formulations that include epoxy resinhaving formula (I), the selection of the diamine curing agent is basedupon distortion behavior performance attributes as the highest rankingcriterion, followed by the following secondary performance attributes inrank descending order: curing reaction control, fluid sorptionresistance (e.g., MEK sorption resistance), resin modulus, and Tg (glasstransition temperature). Each of these performance attributes aredescribed in greater detail below.

Distortional Performance-Von Mises Strain

The determination of distortion behavior performance and whatconstitutes “good for distortion” index scores of the diamine curingagents presented in Table III can be determined by molecular dynamicssimulation and by experimental test. Distortion as determined bymolecular dynamics simulation can be quantified by a measurement of theequivalent strain at yield or the point of peak stress on thestress-strain curve. For this analysis, one performs a uni-directionalcompression loading tracking the equivalent strain versus the equivalentstress and selects the value of equivalent strain that corresponds tothe zero slope in the stress versus strain plot. One can interpret thisvalue to be equal to the yield condition for the polymer.

Distortion as determined by experimental test can be done with a 10degree lamina coupon and use the finite element method withmicromechanical enhancement to determine the values of the trace of thestrain tensor at the critical point (highest value). The von Misesequation is then used with the obtained data to calculate the criticalvalue.

These methods are well known in the an, as reflected by works by Tran T.D., Kelly D., Prusty B. G., Gosse J. H., Christensen S.,“Micromechanical modeling for onset of distortional matrix damage offiber reinforced composite materials,” Compos. Struct. 2012; 94:745-757and Buchanan D. L., Gosse J. H., Wollschlager J. A., Ritchey A., PipesR. B. “Micromechanical enhancement of the macroscopic strain state foradvanced composite materials,” Compos. Sci. Technol, 2009; 69:1974-1978,the contents of both which are incorporated by reference for theirrespective teachings.

Accordingly, molecular dynamics simulations were performed in which theepoxy and diamine curing agent were varied in a systematic fashion toelucidate the effect of the particular formulation change on thedistortional deformation capacity. Selected systems were also tested byexperiment to verify the accuracy of the molecular dynamic simulations.A summary of von Mises strain values determined for these systems ispresented in Table IV, which demonstrates that the simulations providegood agreement with tests for determining von Mises strain values.

TABLE IV von Mises strain values for thermoset formulations withdifferent diamine curing agents¹ Epoxy Resin (XVII) (m-BAPS) (V)(ABP133) (XIV) (33DDS) D.E.N. 431 [0.468]; 0.342 [0.503]; 0.37  [0.413];0.345   0.345 0.315 Tactix 123 [0.32]; 0.31 [0.32]; 0.29 [0.27]; 0.3450.332 Tactix 556 [0.38] [0.36]; 0.25 [0.17]  0.24 PY 306 [0.31] [0.27][0.25]; 0.22  0.27  ¹For thermosets containing a given epoxy resin witheach diamine curing agent, the first line of data represents von Misesvalues based upon molecular dynamics simulations (bracketed valuesreflect one configuration; bolded values reflect the average of fiveconfigurations) and the second line of data (where applicable) reflectvon Mises values based upon experimental test.

Table V summaries the actual von Mises values corresponding to therelative rankings of distortional performance attributes for the diaminecuring agents of Table III.

TABLE V von Mises strain values correspondences for relative rankings ofTable IV. Ranking von Mises Value Strain Values¹ 1 — 2 0.18-0.23 30.24-0.30 4 0.31-0.35 5 >0.35 ¹von Mises strain values are reported as arange of values.

Exemplary diamine curing agents having high distortional propertiesinclude those having a plurality of coupled aromatic ring groups (forexample, three aromatic ring groups), such as formulas (V), (VI),(VIII)-(XIII), and (XVII)-(XXIV).

Curing Reaction Control Performance

The reactivity of the amine curing agent, both in terms of reactionkinetics and temperature-dependence of reactivity, correlatesapproximately with the nucleophilicity of the amino groups of thediamines. To assess reaction control for curing by a given diaminecuring agent, one can perform quantum simulations to determine theelectron distribution and to calculate a reactivity index known as theFukui index. The technique measures the atom affinity to be the site ofeither an electrophilic or nucleophilic attack. The amine is anucleophile and would be susceptible to an electrophilic attack, so theFukui (F⁻) index was determined and compared with pK_(b) measurements tofirst calibrate the simulation technique and then used in the methodwith amines for which no basicity values could be found to rankreactivity in an S_(N)2 reaction that would lead to the polymerization.Amine basicity and reactivity are directly proportional so the Fukuiindex can be used to measure the inductive and resonance effects of thearomatic ring and any electron donating or withdrawing substituentsfavorably or unfavorably placed as a comparative indicator of reactionpotential. Reactivity data, Fukui index data and pK_(b) values arepresented for different diamine curing agents in comparison to thereactivity of diamine curing agent having the formula (II) (44DDS) arepresented in Table VI.

TABLE VI Fukui electrophilic indices, predicted pKb values and relativereactivity of exemplary diamine curing agents Fukui ElectrophilicPredicted Relative Formula Index¹ pK_(b) ¹ Reactivity^(1, 2) (II) 0.04613 1.000 (44DDS) 0.082 13 1.000 (III) 0.076 11.83174 14.732 (MDA) 0.08512.89277 1.280 (V) 0.063 12.33798 4.592 (APB133) 0.071 13.39319 0.404(VIII) 0.091 11.24761 56.545 (DANPG) 0.104 12.21363 6.115 (XIV) 0.081511.61756 24.124 (33DDS) 0.0850 12.89277 1.280 (XVII) 0.0655 12.240635.746 (3BAPS) 0.0725 13.33957 0.458 (XXIII) 0.0655 12.24063 5.746 (BAPS)0.0720 13.35744 0.439 (XXIV) 0.0535 12.70793 1.959 (BAPP) 0.059513.80424 0.157 ¹First line entries reflect Mulliken-based correlationsand second line entries reflect Hirshfeld-based correlations.²Reactivity relative to diamine curing agent of formula (II).

Table VII summarizes the curing reaction control values corresponding tothe relative rankings of reaction control for curing performanceattributes for the diamine curing agents of Table III.

TABLE VII Reaction control correspondences for relative rankings ofTable VI Ranking Curing Reaction Value Control Values, k¹ 1 k > 55 2  24< k ≦ 55 3   8 < k ≦ 24 4  2 < k ≦ 8 5 1 ≦ k ≦ 2 ¹Curing reactioncontrol is expressed as relative reactivity in comparison to diaminecuring agent of formula (II) (44DDS) using the Mulliken-basedcorrelations for the indicated ranges.

The ranking values summarized in Table VII provide a useful guide torefine selection of appropriate diamine curing agents for distortionalthermoset formulations including epoxy resins of formula (I). Additionalconsiderations based on chemical knowledge and experience from empiricalstudies can lead to further refinement in the selection of diaminecuring agent. For example, certain diamine curing agents presented inTable III have a reduced relative score than suggested from the datapresented in Table VI, owing to the fact that they display greaterreactivity towards epoxy resins (see, for example, formula (V)).

Exemplary diamine curing agents include those that possess chemicallatency properties, such as remaining stable at ambient temperature andonly promote curing at an elevated temperature. Such diamine curingagents typically include reactive amino groups having reducednucleophilicity relative to alkyl amines; such diamines can includereactive amino groups conjugated to electron-withdrawing moieties, suchas conjugated aromatic systems, such as aryl moieties, wherein thearomatic systems contain —SO₂, —SO₃H, —NO₂, —CN, —CR₃, wherein R is, forexample, a halide, —CHO, —CO₂H, at the ortho- and para-positionsrelative to the reactive amino group.

Exemplary diamine curing agents having slower kinetics of curing includeformulas (II), (XVI)-(XVIII) and (XXIII)-(XXV) of Table III. Exemplarydiamine curing agents having fast kinetics of curing include formulas(III)-(XV) and (XIX)-(XXII) of Tables III.

Fluid Sorption Resistance Performance

An empirical test of fluid sorption resistance is the ability for agiven thermoset composite to absorb Methyl ethyl ketone (MEK). In thistest, a composite containing a thermoset formulation is permitted tosoak in MEK for a period of time, such as from about 3 days to about 30days. Following a soak period, the weight of the composite is obtainedand compared with the weight of the composite prior to beginning thesoak. The percentage increase in weight of the composite following thesoak period reflects the amount of fluid sorption picked up by thecomposite over time. Thermoset formulations that absorb greater thanabout 10% (wt) fluid will have short lifespan under normal useconditions. Exemplary diamine curing agents having high fluid sorptionresistance properties include formulas (II)-(VI), (X), (XII), (XIV),(XVI), (XVIII), (XX) and (XXV).

Table VIII summarizes 30 day MEK weight pick-up for neat resin samples,a process that mimics the composite soaking procedure described above.Relating the neat resin MEK soak data to molecular structure givesinsight to the molecular moieties that affect fluid sorptionperformance. It is observed that the fluid sorption resistance of thepolymer is decreased by the existence of pendant groups and linkagesbetween phenylene rings that undergo facile motion. Alternatively, thefluid sorption resistance of the polymer is increased by the presence ofrigid pendant groups and phenylene ring linkages, which do not undergofacile motion.

TABLE VIII MEK Diffusivity Data Density, 30 day weight gm/cc Materialpick up, % (simulated) BisA/APB133 1.0 1.182 BisA/BisM aniline 3.5BisA/BisP aniline 4.5 BisM/BisM aniline 10+ (3 days) BisM/APB133 15.5 (8days)  1.144 BisM/BisP aniline  11+ (15 days) BisF/MDA 0.33 1.189BisF/BisM aniline 1.42 BisF/APB133 0.4 1.211 BisF/BisP aniline 1.5BisA/BAPS ~1.0 1.210* BisA/mBAPP 2.4 1.155 BisM/mBAPP  13.5 (11 days)BisF/mBAPP 1.0 BisF/BAPS 0.5 1.239* BisA/44DDS 8 1.208* BisS/44DDS 0.2BisF/44DDS 2.0 1.238* BisM/44DDS 1.163* BisF/33DDS 0.5 1.240* BisA/33DDS2.5 1.187*

Resin Modulus and Glass Transition Temperature Performance

The resin modulus performance attributes of the diamine curing agentsrelate to the number of ring systems in their structure, wherein morerings within a given structure tends to reduce the resin modulus.Measurements of the four-ring systems show that Young's modulusdecreased to about 300,000 psi whereas measurements with a two-ringsystem (e.g., formula (II), 44DDS), the Young's modulus isusually >500,000 psi. Similar reasoning pertains to the glass transitiontemperature value, T_(g), wherein a tighter network afforded by thesmaller molecules usually increases intermolecular attractions andresults in a higher T_(g). Since both modulus and T_(g) are influencedby both the diamine curing agent and the epoxy resin, one can onlyprovide trends regarding the diamine curing agent influence onperformance. The relative (1 to 5) ranking of both acceptable resinmodulus and Tg values is reflected in the number of ring groups, whereinthe higher ranking values are found for diamine curing agents havingmore ring groups within their structure. Exemplary diamine curing agentshaving adequate modulus and glass transition temperatures includeformulas (II)-(VII), (XIV), (XVIII) and (XX).

Blending Melting Point Performance

Thermoset formulations can blended by dissolving solid crystalline aminein semi-liquid epoxy. The blending process can require heating the epoxyresin to a moderate temperature (e.g. about 140° F.) and adding thediamine curing agent as a finely ground powder until the mixture isclear. The mixture is then cooled to room temperature and evaluated toascertain whether the diamine curing agent remains in solution, asevidenced by the solution remaining clear and not becoming cloudy. Oneconsideration for dissolution is the melting point temperature of thediamine curing agent. Thus, the relative (1 to 5) ranking of diaminecuring agents is reflected in melting point temperature, wherein thehigher ranking values are found for diamine curing agents having lowermelting point temperatures. For example, formula (XVIII) has a rankingvalue of “1” in blending melting point performance owing to the factthat this diamine curing agent has a melting point temperature of ˜300°C. Exemplary diamine curing agents having a useful melting point forblending include formulas (II)-(VIII), (XIV), (XV) and (XIX).

In terms of distortional thermoset formulations that include the epoxyresin of formula (I), consideration of diamine curing agents exhibitinggood for distortion behavior is important, followed by consideration ofcontrollability of curing reaction kinetics (that is, reaction controlfor curing as depicted in Table III), fluid sorption resistance,acceptable modulus and glass transition temperature values. In someembodiments of thermoset formulations, the epoxy resin of formula (I) iscured with at least one diamine curing agent having good for distortionbehavior, such as a diamine curing agent selected from the groupconsisting of formulas (V), (VI), (VIII)-(XIII), and (XVII)-(XXIV), andcombinations thereof.

In some embodiments, distortional thermoset formulations can include theepoxy resin of formula (I) and a diamine curing agent of any of formulas(II)-(XXV). In some embodiments, distortional thermoset formulations caninclude epoxy resin of formula (I) and the diamine curing agent offormula (V).

In other embodiments, distortional thermoset formulations can includethe epoxy resin of formula (I) and a mixture of two or more diaminecuring agents of any of formulas (II)-(XXV). Distortional thermosetformulations can include epoxy resin of formula (I) and a mixture of twodiamine curing agents, wherein a first diamine curing agent exhibitsslow curing reaction kinetics and a second diamine curing agent exhibitsfast curing reaction kinetics. In some embodiments of distortionalthermoset formulations, the mixture of two diamine curing agentsincludes a first diamine curing agent selected from the group consistingof formulas (II), (XVI)-(XVIII) and (XXIII)-(XXV), and combinationsthereof and a second diamine curing agent selected from the groupconsisting of formulas (III)-(XV) and (XIX)-(XXII), and combinationsthereof.

The relative amounts of the first diamine curing agent and the seconddiamine curing agent are selected to afford reliable control of thekinetics of curing the thermoset formulations including an epoxy resinformula (I). In some embodiments, the mixture of diamine curing agentscan be adjusted to include about 90% (wt) of the first diamine curingagent and about 10% (wt) of the second diamine curing agent.

In one embodiment of a thermoset formulation that includes the epoxyresin of formula (I) and a mixture of two diamine curing agents, thefirst diamine curing agent is formula (II) and the second diamine agentis formula (V). With respect to the mixture of diamine curing agents offormulas (II) and (V), the mixture can be adjusted to include about 90%(wt) of the diamine curing agent of formula (II) and about 10% (wt) ofthe diamine curing agent of formula (V).

Where distortional thermoset formulations include a mixture of two ormore diamine curing agents, it is desirable to adjust the proportions ofthe mixture so that optimal out-life requirements and advantageouscuring reaction kinetics can be achieved. Thus, a highly reactivediamine curing agent can be included in mixtures of diamine curingagents, provided that it represents a sufficiently minor component so asto provide the desired product specifications in distortional thermosetformulations in terms of the desired out-life requirements andadvantageous reaction kinetics. One skilled in the art can readilydetermine optimal recipes for mixtures of two or more diamine curingagents for use in distortional thermoset formulations disclosed herein.Such distortional thermoset formulations provide desirable out-liferequirements, advantageous reaction kinetics for curing mixtures andsuperior mechanical properties.

Prepreg Materials and Compositions

The distortional thermoset formulations can be used to prepare prepregmaterials and compositions. Materials for prepregs include fiberscomposed of graphite, fiberglass, nylon, Kevlar® and related materials(for example, other aramid polymers), spectra, among others. Thedistortional thermoset formulations are typically prepared bysolubilizing the diamine curing agent(s) into the epoxy resin of formula(I) by mixing and thereafter applying the resultant formulation(s) ontoa plurality of fibers or laminates thereof. The term, “applying”includes any deposition method (for example, dipping, coating, spraying,etc.). The distortional thermosets used for generating these fibercomposites can occur typically with a multistep process as desiredaccording to meeting certain engineering logistics and structurebuild-outs. The distortional thermosets disclosed herein possessfavorable reaction kinetics for preparing cured fiber-based prepregcompositions, as defined by at least one of the following features:

-   -   (1) distortional thermoset formulations maintain melt phase at        viscosities conducive to prepreging (that is, forming a prepreg        composition) for 4 or more hours;    -   (2) once the prepreg composition is formed, the viscosity of the        distortional thermoset formulation will not advance (that is,        remain stage B transitional material) when frozen;    -   (3) a thawed prepreg composition remains workable for at least        45 days at ambient temperature and pressure to accommodate the        layup of large engineering structures (for example, aerospace        structures); and    -   (4) the prepreg composition will cure to desired properties in        current autoclave processing conditions (for example, 350° F.        for 3-6 hours).

Comparison to Other Distortional Thermosets Reveals Surprising,Unexpected Properties in Sorption Resistance of Thermosets that IncludeEpoxy Resins of Formula (I)

The distortional thermoset formulations disclosed herein retain theenhanced composite mechanical performances of other distortionalthermosets, including increased distortional deformation and/ordecreased dilation load, as reflected by substantially improved vonMises strains of about 0.300 or greater as compared to conventionalnon-distortional thermosets (von Mises strains in the range from about0.15 to about 0.19). However, the distortional thermoset formulationsdisclosed herein display superior sorption resistance characteristicswhen compared to previously described thermosets. For example, thedistortional thermoset formulations comprising the epoxy resin offormula (I) absorb about 1% (wt) or less of contaminating materials andfluids, such as Methyl ethyl ketone (MEK). By contrast, otherdistortional thermosets absorb up to 100-fold more of contaminatingmaterials and fluids under comparable conditions.

A dramatic illustration of the surprisingly unexpected sorptionproperties of thermosets having the epoxy resin of formula (I) is thesuperior resistance to fluid sorption that the thermoset displays whencompared to a thermoset composition that includes a structurally similarepoxy resin, 1,3-bis(2-(4-(oxiran-2-ylmethoxy)phenyl)propan-2-yl)benzene(BisM) (see Table IX). The differences in the MEK fluid sorptionresistance properties are not obvious from inspection of the chemicalstructures of BisX and BisM alone.

TABLE IX von Mises strains and MEK sorption resistance in differentthermosets. Von Mises MEK Name Structure of Epoxy Resin of Thermoset¹strain data sorption BisX (formula (I))

>0.300 ≦1% (wt) BisM²

>0.300 ≧15% (wt) ¹Both thermoset formulations include diamine curingagent of formula (II) (44DDS) in a 1:1 stoichiometric ratio with therespective epoxy resins. ²See U.S. Pat. Nos. 7,745,549 and 7,985,808.

Thus, prepreg compositions that include the distortional thermosetcompositions disclosed herein afford comparable composite mechanicalperformances of other distortional thermosets, yet provide surprisinglyrobust fluid sorption resistance attributes not found in prior artdistortional thermosets. Such qualities may provide improvedperformance, reduced weight, and reduced failure onsets over thelifetime of the prepreg composites that include the distortionalthermosets disclosed herein. Furthermore, the formulations for thedistortional thermosets disclosed herein have improved out-liferequirements and advantageous reaction kinetics, rendering theformulations more reliable for preparing prepreg composite materials andstructures.

To the extent that the present application references a number ofdocuments, those documents are hereby incorporated by reference hereinin their entirety.

While the present disclosure has been described with reference tocertain embodiments, it will be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the scope of the present disclosure. In addition,modifications may be made to adapt a particular situation or material tothe teachings of the present disclosure without departing from itsscope. Therefore, it is intended that the present disclosure not belimited to the particular embodiment disclosed, but that the presentdisclosure will include all embodiments falling within the scope of theappended claims.

What is claimed is:
 1. A composition, comprising one or more reactionproducts of an amount of: an epoxy resin of formula (I):

and a first diamine curing agent.
 2. The composition of claim 1, whereinthe composition has a von Mises strain of at least 0.300.
 3. Thecomposition of claim 1, wherein the diamine curing agent is selectedfrom the group consisting of formulas (II)-(XXV):

and combinations thereof.
 4. The composition of claim 1, wherein theepoxy resin of formula (I) is


5. The composition of claim 1, wherein the epoxy resin of formula (I) is


6. The composition of claim 1, wherein the epoxy resin of formula (I) is


7. The composition of claim 1, wherein the epoxy resin of formula (I) is


8. The composition of claim 1, wherein the epoxy resin of formula (I) is


9. The composition of claim 1, wherein the epoxy resin of formula (I) is


10. The composition of claim 1, wherein the epoxy resin of formula (I)is in stoichiometric excess relative to the diamine curing agent. 11.The composition of claim 1, wherein the diamine curing agent has a Fukuielectrophilic index between about 0.04 and about 0.06.
 12. Thecomposition of claim 1, further comprising a second diamine curingagent.
 13. The composition of claim 12, wherein the first diamine curingagent is 4,4′-sulfonyldianiline.
 14. The composition of claim 13,wherein the second diamine curing agent has a curing reaction controlvalue between about 1 and about 55 as relative reactivity compared to4,4′-sulfonyldianiline by Mulliken-based correlations.
 15. Thecomposition of claim 12, wherein the second diamine curing agent has acuring reaction control value between about 1 and about 55 as relativereactivity compared to 4,4′-sulfonyldianiline by Mulliken-basedcorrelations.
 16. The composition of claim 15, wherein the seconddiamine curing agent has a curing reaction control value between about 1and about 8 as relative reactivity compared to 4,4′-sulfonyldianiline byMulliken-based correlations.
 17. The composition of claim 16, whereinthe first diamine curing agent has a curing reaction control valuebetween about 24 and about 55 as relative reactivity compared to4,4′-sulfonyldianiline by Mulliken-based correlations.
 18. Thecomposition of claim 1, wherein the first diamine curing agent comprisesat least one electron-withdrawing moiety.
 19. The composition of claim18, wherein the at least one electron-withdrawing moiety is selectedfrom the group consisting of: —SO₂, —SO₃H, —NO₂, —CN, —CR₃, —CHO, and—CO₂H, wherein R is a halide.
 20. The composition of claim 12, whereinthe second diamine curing agent comprises at least oneelectron-withdrawing moiety.
 21. The composition of claim 20, whereinthe at least one electron-withdrawing moiety of the second diaminecuring agent is selected from the group consisting of: —SO₂, —SO₃H,—NO₂, —CN, —CR₃, —CHO, and —CO₂H, wherein R is a halide.
 22. Thecomposition of claim 20, wherein the first diamine curing agentcomprises at least one electron-withdrawing moiety.
 23. The compositionof claim 22, wherein the at least one electron-withdrawing moiety isselected from the group consisting of: —SO₂, —SO₃H, —NO₂, —CN, —CR₃,—CHO, and —CO₂H, wherein R is a halide.
 24. The composition of claim 12,wherein a ratio of first diamine curing agent to second diamine curingagent is about 9:1 by weight.
 25. The composition of claim 1, whereinthe first diamine curing agent has three ring groups.
 26. Thecomposition of claim 12, wherein the first diamine curing agent isselected from the group consisting of 4,4′-sulfonyldianiline,4,4′-thiodianiline,3,3′-((sulfonylbis(4,1-phenylene))bis(oxy))dianiline,4,4′-(1,4-phenylenedisulfonyl)dianiline,4,4′-((sulfonylbis(4,1-phenylene))bis(oxy))dianiline,4,4′-((propane-2,2-diylbis-(4,1-phenylene))bis(oxy))-dianiline, and4,4′disulfanediyldianiline; and wherein the second diamine curing agentis selected from the group consisting of 4,4′-methylenedianiline,4,4′-oxydianiline, 3,3′-(1,3-phenylenebis(oxy))-dianiline,4,4′-(1,3-phenylenebis(oxy))-dianiline,4,4′-methylenebis(2-ethyl-aniline), 4,4′-methylenebis(2-ethyl-aniline),3,3′-((2,2-dimethylpropane-1,3-diyl)bis(oxy))dianiline,4,4′-(1,4-phenylenebis-(propane-2,2-diyl))dianiline,3-(4-(4-aminobenzyl)-benzyl)aniline,4,4′-(1,4-phenylenebis(propane-2,2-diyl))bis(2,6-dimethylaniline),4,4′-(1,4-phenylenebis(oxy))-dianiline,3,3′-((propane-2,2-diylbis-(4,1phenylene))bis(oxy))-dianiline,3,3′-sulfonyldianiline, 4,4′-methylenebis(cyclo-hexan-1-amine),4,4′-(pentane-1,5-diylbis-(oxy))dianiline,4,4′-([1,1′-biphenyl]-4,4′-diylbis(oxy))dianiline,4,4′-(1,3-phenylenebis-(propane-2,2-diyl))bis(2,6-diisopropylaniline),and 4,4′-(1,3-phenylenebis-(propane-2,2-diyl))dianiline.
 27. Thecomposition of claim 26, wherein a ratio of first diamine curing agentto second diamine curing agent is about 9:1 by weight.
 28. Thecomposition of claim 1, further comprising one or more fibers.
 29. Thecomposition of claim 28, wherein the one or more fibers is selected fromthe group consisting of graphite, fiberglass, nylon, aramids, aramidpolymers, and spectra.